Fluorescent diketopyrrolopyrroles

ABSTRACT

The present invention relates to fluorescent diketopyrrolopyrrole of the formula (I), a process for their preparation and their use for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners, as fluorescent tracers, in color changing media, in solid dye lasers and electroluminescent devices. A luminescent device comprising a composition according to the present invention is high in the efficiency of electrical energy utilisation and high in luminance.

The present invention relates to fluorescent diketopyrrolopyrroles(DPPs) of the formula I

a process for their preparation and their use for the preparation ofinks, colorants, pigmented plastics for coatings, non-impact-printingmaterial, color filters, cosmetics, polymeric ink particles, toners, asfluorescent tracers, in color changing media, dye lasers andelectroluminescent devices. A luminescent device comprising a compoundaccording to the present invention is high in the efficiency ofelectrical energy utilisation and high in luminance.

EP-A-648770 relates to DPPs containing carbamate groups and their use asfluorescence dyestuff. In Examples 6 and 9 the following DPP compoundsare disclosed:

respectively.

WO90/01480 relates to substances, among others DPP compounds, with atleast two different coloured forms, one of which can be converted to theother by supplying energy and their use in storage media. In Examples 10and 11 the following DPP compounds are disclosed

respectively.

It is presently common to prepare organic electroluminescent (“EL”)devices which contain an organic fluorescent substance by a vacuumevaporation process, e.g. described in Appl. Phys. Lett., 51, 913(1987). In general, two types of such vacuum evaporation processes areapplied according to the constitution of light emitting material: aone-component type process and a two-component type (or “Host-Guesttype” or binary systems) process (e.g. described in J. Appl. Phys., 65,3610 (1989)).

JP-A2 2,296,891 (Ricoh) claims an electroluminescent element comprisinga positive electrode, a negative electrode and one organic compoundlayer or a plurality of organic compound layers held between thepositive and negative electrodes, but no hole transporting substance. Atleast one layer of said organic compound layers is a layer containing apyrrolopyrrole compound represented by the following formula II″

wherein Y₁ and Y₂ independently from each other represent a substitutedor unsubstituted alkyl, cycloalkyl or aryl group, Y₃ and Y₄independently represent a hydrogen atom or a substituted orunsubstituted alkyl or aryl group, and X represents an oxygen or asulfur atom. Four compounds are mentioned explicitly, namely wherein Xstands for oxygen In all cases, and wherein (a) Y₃=Y₄=methyl andY₁=Y₂=p-tolyl, (b) Y₃=Y₄=methyl and Y₁=Y₂=hydrogen, (c) Y₃=Y₄=hydrogenand Y₁=Y₂=p-tolyl, and (d) Y₃=Y₄=Y₁=hydrogen and Y₂=p-chlorophenyl. Noemission is observed, if DPP II″ is used alone, i.e. without theaddition of tris(8-hydroxyquinolinato)aluminium (“Alq₃”).

JP-A2 5,320,633 (Sumitomo) claims an organic EL device having a lightemitting layer comprising a light emitting material in an amount of0.005 to 15 parts by weight of a DPP of the formula

between a pair of electrodes, wherein at least one electrode beingtransparent or semi-transparent, wherein Y₁ and Y₂ independently of eachother stand for a C₆-C₁₄-aryl group or a C₆-C₁₂heterocyclic group, suchas thienyl, 2-pyridyl, 3-pyridyl and 4-pyridyl, and Y₃ and Y₄independently of each other stand for a hydrogen atom, a C₁-C₁₂-alkylgroup or a C₆-C₁₄aryl group. Although the main claim is silent about theuse of Alq₃, it is clear from the specification and the examples,especially from comparative example 2, that Alq₃ is an essential featurein the claimed EL element or device.

JP-A2 9003448 (Toyo) describes an organic EL element having between apair of electrodes a luminous layer containing a DPP-compound aselectron-transporting material or an organic compound thin film layerincluding a luminous layer and an electron-injecting layer wherein theelectron-injecting layer contains a DPP compound as theelectron-transporting material. The following threeheteroarylpyrrolopyrroles are explicitly mentioned:

The disadvantage of the claimed EL devices is that according to theexamples always Alq₃ and a phenanthrene diamine (as hole-injectingmaterial) have to be used.

EP-A-499,011 describes electroluminescent devices comprisingDPP-compounds of the formula

wherein Y₁ and Y₂ can be a substituted or unsubstituted phenyl group, a3-pyridyl- or 4-pyridylgroup and Y₃ and Y₄ independently of each otherstand for a hydrogen atom, a C₁-C₁₈-alkyl group, an C₃-C₁₈alkenyl groupand the double bond not being the C₁-position. In example 1 and 7 thefollowing DPP compounds are explicitly mentioned

WO98/33862 describes the use of the DPP-compound of formula IV′

as a guest molecule in electroluminescent devices.

EP-A-1087005 relates to fluorescent N-substituted diketopyrrolopyrroles(“DPPs”) of the formula I′

characterized in that Y¹ and Y² are derived from the following groups:

example

which can be substituted or unsubstituted.

EP-A-1087006 relates to an electroluminescent device comprising in thisorder (a) an anode, (b) a hole transporting layer, (c) a light-emittinglayer, (d) optionally an electron transporting layer and (e) a cathodeand a light-emitting substance, wherein the light-emitting substance isa diketopyrrolopyrrole (“DPP”) represented by formula I′.

WO03/002672 relates to diketopyrrolopyrroles of formula I′ characterizedin that Y¹ and Y² are derived from the following 1-naphthyl group:

PCT/EP03/00650 discloses EL devices comprising a DPP guest chromophoreof formula IV and a DPP host chromophore of formula II (see below).

EP-A-1,253,151 discloses EL devices comprising at least one of

(a) a DPP derivative and an organic fluorescent material having afluorescent peak wavelength in the range of 580 to 720 nm and

(b) a pyrromethene metal complex (see also JP2001 257077, JP2001 257078,and JP2001 297881 (Toray))

WO03/048268 relates to compositions for EL elements, comprising acompound having a perylene ring and a compound having a DPP skeleton.The following three heteroarylpyrrolopyrroles are explicitly mentioned:

Surprisingly, it was found that luminescent devices, which are high inthe efficiency of electrical energy utilisation and high in luminance,can be obtained if specific DPP compounds or specific combinations ofDPP compounds are used, especially as light emitting substances.

Accordingly, the present invention relates to fluorescentdiketopyrrolopyrrole of the formula I

R¹ and R² may be the same or different and are selected from aC₁-C₂₅alkyl group, which can be substituted by fluorine, chlorine orbromine, an allyl group, which can be substituted one to three timeswith C₁-C₄alkyl, a cycloalkyl group, or a cycloalkyl group, which can becondensed one or two times by phenyl which can be substituted one tothree times with C₁-C₄-alkyl, halogen, nitro or cyano, an alkenyl group,a cycloalkenyl group, an alkynyl group, a haloalkyl group, a haloalkenylgroup, a haloalkynyl group, a ketone or aldehyde group, an ester group,a carbamoyl group, a ketone group, a silyl group, a siloxanyl group, A³or —CR³R⁴—(CH₂)_(m)-A³ whereinR³ and R⁴ independently from each other stand for hydrogen orC₁-C₄alkyl, or phenyl which can be substituted one to three times withC₁-C₄alkyl,A³ stands for aryl or heteroaryl, In particular phenyl or 1- or2-naphthyl which can be substituted one to three times with C₁-C₈alkyland/or C₁-C₈alkoxy, and m stands for 0, 1, 2, 3 or 4,A¹ and A² are Independently of each other a group comprising afive-membered heterocyclic ring, containing one to three heteroatomsselected from the group of nitrogen, oxygen and sulfur, or asix-membered heterocyclic ring, containing one to three heteroatomsselected from the group of nitrogen, oxygen and sulfur, wherein, if A¹and A² are a single five- or six-membered heterocyclic ring of formula

said heterocyclic ring is substituted by at least a group selected froma C₁-C₂₅alkyl group, a cycloalkyl group, an aralkyl group, an alkenylgroup, a cycloalkenyl group, an alkynyl group, a hydroxyl group, amercapto group, an alkoxy group, an alkylthio group, an aryl ethergroup, an aryl thioether group, an aryl group, a heterocyclic group, ahalogen atom, a haloalkyl group, a haloalkenyl group, a haloalkynylgroup, a cyano group, an aldehyde group, a carboxyl group, an estergroup, a carbamoyl group, a nitro group, a silyl group, a siloxanylgroup, a substituted or unsubstituted vinyl group, a group NR⁸R⁹,wherein R⁸ and R⁹ independently of each other stand for a hydrogen atom,an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, aheterocyclic group, an aralkyl group, or R⁸ and R⁹ together with thenitrogen atom to which they are bonded form a five or six memberedheterocyclic ring, which can be condensed by one or two optionallysubstituted phenyl groups, wherein the heterocyclic ring is directlybonded to the DPP basis unit, especially

A¹ and A² are independently of each other a group

R⁵, R⁶, and R⁷ may be the same or different and are selected from ahydrogen atom, a C₁-C₂₅alkyl group, a cycloalkyl group, an aralkylgroup, an alkenyl group, a cycloalkenyl group, an alkynyl group, ahydroxyl group, a mercapto group, an alkoxy group, an alkylthio group,an aryl ether group, an aryl thioether group, an aryl group, aheterocyclic group, a halogen atom, a haloalkyl group, a haloalkenylgroup, a haloalkynyl group, a cyano group, an aldehyde group, a carboxylgroup, an ester group, a carbamoyl group, a nitro group, a silyl group,a siloxanyl group, a substituted or unsubstituted vinyl group, a groupNR⁸R⁹, wherein R⁸ and R⁹ independently of each other stand for ahydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, aheteroaryl group, a heterocyclic group, an aralkyl group, or R⁸ and R⁹together with the nitrogen atom to which they are bonded form a five orsix membered heterocyclic ring, which can be condensed by one or twooptionally substituted phenyl groups, or at least two adjacentsubstituents R⁵ to R⁷ form an aromatic or aliphatic fused ring system,and X¹ is a hydrogen atom, a C₁-C₂₅alkyl group, a cycloalkyl group, anaralkyl group, an aryl group, or a heterocyclic group, with the proviso,that the following compounds are

are excluded.

A¹ and A² can be different, but are preferably the same. If A¹ and A²are a group of formula

they are preferably a group of formula

wherein R^(5′) is R⁵ except hydrogen.

In a preferred embodiment of the present invention at least one of thegroups R⁵, R⁶, and R⁷ is different from a hydrogen atom, if A¹ and A²are a single five- or six-membered heterocyclic ring, containing oneheteroatom selected from the group of nitrogen, oxygen and sulfur.

In another preferred embodiment of the present invention at least one ofthe groups R⁵, R⁶ and R⁷ is different from a hydrogen atom.

Preferably R¹ and R² independently from each other are selected fromC₁-C₁₄alkyl, C₅-C₁₂ cycloalkyl, especially cyclohexyl, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, orC₅-C₁₂-cycloalkyl, especially cyclohexyl, which can be condensed one ortwo times by phenyl, which can be substituted one to three times withC₁-C₄-alkyl, halogen, nitro or cyano, phenyl or 1- or 2-naphthyl whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, or —CR³R⁴—(CH₂)_(m)-A³ wherein R³ and R⁴ stand forhydrogen, A³ stands for phenyl or 1- or 2-naphthyl, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and mstands for 0 or 1.

Preferably A¹ and A² independently from each other are selected from

whereinR⁵ is a hydrogen atom, a C₁-C₁₂alkyl group, a C₁-C₈alkoxy group, a groupof formula

or a group —NR⁸R⁹, wherein R⁸ and R⁹ independently from each other standfor C₁-C₈alkyl group, A¹, such as

especially

or R⁸ and R⁹ together with the nitrogen atom to which they are bondedform a five or six membered heterocyclic ring, such as

which can be condensed by one or two optionally substituted phenylgroups, such as

wherein R¹⁵, R¹⁶ and R¹⁷ independently from each other stands forhydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, or phenyl, R^(5′) is R⁵, excepthydrogen, R^(5″) and R^(6″) independently from each other stands forhydrogen, C₁-C₈-alkyl or C₁-C₈-alkoxy, and X¹ stands for hydrogen, orC₁-C₈-alkyl.

The following diketopyrrolopyrroles are preferred:

especially

especially

especially

especially

especially

wherein R¹ and R² are independently of each other a C₁-C₁₂alkyl group,such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl,isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, a C₅-C₇cycloalkyl group, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, or which can be condensed one or two times by optionallysubstituted phenyl, especially

wherein R⁵¹, R⁵² and R⁵³ are independently of each other hydrogen,C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, or a C₇-C₁₄aralkyl group,such as —CR³R⁴—(CH₂)_(m)-A³ wherein R³ and R⁴ stand for hydrogen, A³stands phenyl, biphenyl or 1- or 2-naphthyl which can be substituted oneto three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and m stands for 0 or1, such as C₁-C₈alkylphenyl, di(C₁-C₈alkyl)phenyl, in particular3-methylphenyl, 4-methylphenyl, 3,5-dimethylphenyl,3,5-di-tert.-butylphenyl and 2,5- and 2,6-diisopropylphenyl, wherein thefollowing diketopyrrolopyrroles are especially preferred:

A further preferred embodiment of the present Invention is directed tocompositions comprising a guest chromophore and a host chromophore,wherein the absorption spectrum of the guest chromophore overlaps withthe fluorescence emission spectrum of the host chromophore, wherein thehost chromophore is a diketopyrrolopyrrole having a photoluminescenceemission peak at 500 to 720 nm, preferably 520 to 630 nm, most preferred540 to 600 nm and wherein the host choromophore and/or the guestchromophore is a diketopyrrolopyrrole of formula I. That means, specifichost choromophores of formula I can be used in combination with specificguest choromophores of formula I or guest choromophores of formula IV,and specific guest choromophores of formula I can be used In combinationwith specific host choromophores of formula II.

In one embodiment of the present invention, the compositions comprise ahost chromophore, which is a diketopyrrolopyrrole having aphotoluminescence emission peak at 500 to 720 nm, preferably 520 to 630nm, most preferred 540 to 600 nm and the guest chromophore is adiketopyrrolopyrrole of formula I.

In this embodiment the host chromophore is preferably adiketopyrrolopyrrole (“DPP”) represented by formula II

wherein R¹³ and R¹⁴ Independently from each other stand forC₁-C₂₅-alkyl, which can be substituted by fluorine, chlorine or bromine,C₅-C₁₂-cycloalkyl or C₅-C₁₂cycloalkyl which can be condensed one or twotimes by phenyl which can be substituted one to three times withC₁-C₄-alkyl, halogen, nitro or cyano, silyl, A⁶ or—CR¹¹R¹²—(CH₂)_(m)-A⁶, wherein R¹¹ and R¹² independently from each otherstand for hydrogen, fluorine, chlorine, bromine, cyano or C₁-C₄alkyl,which can be substituted by fluorine, chlorine or bromine, or phenylwhich can be substituted one to three times with C₁-C₄alkyl, A⁶ standsfor phenyl or 1- or 2-naphthyl which can be substituted one to threetimes with C₁-C₈alkyl, C₁-C₈alkoxy, halogen, nitro, cyano, phenyl, whichcan be substituted with C₁-C₈alkyl or C₁-C₈alkoxy one to three times,—NR²³R²⁴, wherein R²³ and R²⁴ represent hydrogen, C₁-C₂₅-alkyl,C₅-C₁₂-cycloalkyl or C₆-C₂₄-aryl, in particular phenyl or 1- or2-naphthyl which can be substituted one to three times with C₁-C₈alkyl,C₁-C₈alkoxy, halogen or cyano, or phenyl, which can be substituted withC₁-C₈alkyl or C₁-C₈alkoxy one to three times, and m stands for 0, 1, 2,3 or 4,A⁴ and A⁵ independently from each other stand for

whereinR²⁵, R²⁶, R²⁷ independently from each other stands for hydrogen,C₁-C₂₅-alkyl, —CR¹¹R¹²—(CH₂)_(m)-A⁸, cyano, halogen, —OR²⁹,—S(O)_(p)R³⁰, or phenyl, which can be substituted one to three timeswith C₁-C₈alkyl or C₁-C₈alkoxy, wherein R²⁹ stands for C₁-C₂₅-alkyl,C₅-C₁₂-cycloalkyl, —CR¹¹R¹²—(CH₂)_(m)-Ph, C₆-C₂₄-aryl, or a saturated orunsaturated heterocyclic radical comprising five to seven ring atoms,wherein the ring consists of carbon atoms and one to three hetero atomsselected from the group consisting of nitrogen, oxygen and sulfur, R³⁰stands for C₁-C₂₅-alkyl, C₅-C₁₂-cycloalkyl, —CR¹¹R¹²—(CH₂)_(m)-Ph, R²⁸stands for C₂-C₂₀-heteroaryl, C₆-C₂₄-aryl, p stands for 0, 1, 2 or 3, mand n stands for 0, 1, 2, 3 or 4.

R¹³ and R¹⁴ independently of each other stand, preferably, forC₁-C₈alkyl, C₅-C₁₂-cycloalkyl, which can be substituted one to threetimes with C₁-C₈alkyl and/or C₁-C₈alkoxy, phenyl or 1- or 2-naphthylwhich can be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, or —CR¹¹R¹²—(CH₂)_(m)-A⁶ wherein R¹¹ and R¹² stand forhydrogen, A⁶ stands for phenyl or 1- or 2-naphthyl, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and mstands for 0 or 1.

A⁴ and A⁵ independently from each other stand, preferably, for

wherein R²⁵ is C₁-C₈-alkyl, phenyl, 1- or 2-naphthyl.

In another preferred embodiment of the present invention, thecompositions comprise a host chromophore, which is adiketopyrrolopyrrole of formula I, and a guest chromophore, which is adiketopyrrolopyrrole of formula IV

wherein R¹³ and R¹⁴ are as defined above, andA⁹ and A¹⁰ independently from each other stand for

R³⁵ and R³⁶ independently from each other stands for hydrogen,C₁-C₂₅-alkyl, C₁-C₂₅-alkoxy, —CR¹¹R¹²—(CH₂)_(m)-A⁶, cyano, halogen,—OR⁴⁰, —S(O)_(p)R⁴¹, or phenyl, which can be substituted one to threetimes with C₁-C₈alkyl or C₁-C₈alkoxy, wherein R⁴⁰ stands forC₁-C₂₅-alkyl, C₅-C₁₂-cycloalkyl, —CR¹¹R¹²—(CH₂)_(m)-Ph, C₆-C₂₄-aryl, ora saturated or unsaturated heterocyclic radical comprising five to sevenring atoms, wherein the ring consists of carbon atoms and one to threehetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, R⁴¹ stands for C₁-C₂₅-alkyl, C₅-C₁₂-cycloalkyl,—CR¹¹R¹²—(CH₂)_(m)-Ph, p stands for 0, 1, 2 or 3, m and n stands for 0,1, 2, 3 or 4,R³⁸ and R³⁹ independently from each other stand for hydrogen,C₁-C₂₅-alkyl, C₅-C₁₂-cycloalkyl, —CR¹¹R¹²—(CH₂)_(m)-A⁶, C₆-C₂₄-aryl, inparticular A⁶, or a saturated or unsaturated heterocyclic radicalcomprising five to seven ring atoms, wherein the ring consists of carbonatoms and one to three hetero atoms selected from the group consistingof nitrogen, oxygen and sulfur, such as A¹, especially

wherein R^(5″) and R^(6″) independently from each other stands forhydrogen, C₁-C₈alkyl or C₁-C₈-alkoxy, or R³⁸ and R³⁹ together with thenitrogen atom to which they are bonded form a five or six memberedheterocyclic ring which can be condensed by one or two optionallysubstituted phenyl groups, such as

and R³³ and R³⁴ independently from each other stand for hydrogen andC₆-C₂₄-aryl, in particular phenyl, wherein R¹¹, R¹² and A⁶ are asdefined above.

If A⁹ and A¹⁰ Independently from each other stand for a group of theformula

R³⁵ and R³⁶ are preferably hydrogen, R³⁸ is preferably C₁-C₆alkyl orphenyl and R³³ and R³⁴ are preferably hydrogen or phenyl.

If A⁹ and A¹⁰ independently from each other stand for a group of theformula

R³⁵ and R³⁶ are preferably hydrogen and R³⁸ is preferably C₁-C₆alkyl orphenyl.

In particular A⁹ and A¹⁰ independently of each other stand for

wherein R³⁵ and R³⁶ independently from each other stand for hydrogen,C₁-C₈-alkyl, C₁-C₈-alkoxy, —CR¹¹R¹²—(CH₂)_(m)-A⁶, cyano, chloro, —OR⁴⁰,or phenyl, which can be substituted one to three times with C₁-C₈alkylor C₁-C₈alkoxy, wherein R⁴⁰ stands for C₁-C₈-alkyl, or C₆-C₂₄-aryl, suchas phenyl, 1-naphthyl or 2-naphthyl, R¹¹ and R¹² are hydrogen orC₁-C₄alkyl, m is 0 or 1, A⁶ is phenyl, 1-naphthyl or 2-naphthyl, R³⁸ andR³⁹ independently from each other stand for hydrogen, C₁-C₈alkyl,C₅-C₁₂-cycloalkyl, In particular cyclohexyl, —CR¹¹R¹²—(CH₂)_(m)A⁶,C₆-C₂₄-aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl,phenanthryl, terphenyl, pyrenyl, 2- or 9-fluorenyl or anthracenyl,preferably C₆-C₁₂aryl such as phenyl, 1-naphthyl, 2-naphthyl,4-biphenyl, which may be unsubstituted or substituted, especially byone, or two C₁-C₈-alkyl, or C₁-C₈alkoxy groups, in particular A⁶, or asaturated or unsaturated heterocyclic radical comprising five to sevenring atoms, wherein the ring consists of carbon atoms and one to threehetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, especially A¹, or R³⁸ and R³⁸ together with the nitrogen atom towhich they are bonded form a five or six membered heterocyclic ringwhich can be condensed by one or two optionally substituted phenylgroups, such as

In particular groups of the following formula are preferred

wherein R³⁸ and R³⁹ independently of each other stand for A¹, especially

or a group of the formula

wherein R⁴¹, R⁴² and R⁴³ are independently of each other hydrogen,C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-C₈alkoxy,C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, an aldehydegroup, a ketone group, a carboxyl group, an ester group, a carbamoylgroup, an amino group, a nitro group, a silyl group or a siloxanylgroup, or R³⁸ and R³⁹ together with the nitrogen atom to which they arebonded form the following condensed ring system

Preferably R⁴¹, R⁴² and R⁴³ are independently of each other hydrogen,C₁-C₈alkyl, C₁-C₈alkoxy or C₁-C₈alkylthio.

The weight ratio of the host chromophore to the guest chromophore is ingeneral 50:50 to 99.99:0.01, preferably 90:10 to 99.99:0.01, morepreferably 95:5 to 99.9:0.1, most preferred 98:2 to 99.9:0.1.

Compounds of formula I, wherein A¹ and A² Independently from each otherare selected from

whereinR⁵ is a hydrogen atom, a C₁-C₁₂alkyl group, a C₁-C₈alkoxy group, a groupof formula

wherein R¹⁵, R¹⁶ and R¹⁷ independently from each other stands forhydrogen, C₁-C₈-alkyl or C₁-C₈-alkoxyR^(5′) is R⁵, except hydrogen, andX¹ stands for hydrogen, or C₁-C₈-alkyl; are preferred as host compounds.

Particularly preferred as host chromophores are the DPP compoundsrepresented by the formula I or II, which are listed below: Com- pound(of for- mula II) A⁴ = A⁵ R¹³ = R¹⁴ H-1 

H-2 

CH₃, H-3 

H-4 

CH₃, H-5  ″ —CH(CH₃)₂ H-6  ″ —(CH₂)₃CH₃ H-7 

H-8 

—Si(CH₃)₃ H-9 

H-10

H-11

H-12

H-13

—CH(CH₃)₂ H-15

H-16

H-16

H-17

—CH(CH₃)₂ H-18

H-19

H-20

H-21

H-22

—CH₃ H-23 ″ —CH(CH₃)₂ H-24 ″

H-25 ″ n-CH₁₂H₂₅ H-26 —CH₂F H-27 ″

H-28 ″

H-29 ″

Com- pound (of for- mula I) A¹ = A² R¹ = R² H-30

—CH₃ H-31

—CH(CH₃)₂ H-32

H-33

—CH₃ H-34 ″ —CH(CH₃)₂ H-35

—CH₃ H-36

—CH₃ H-37

—CH(CH₃)₂ H-38

—CH₃ H-39

—CH₃ H-40

—CH(CH₃)₂ H-41

—CH₃ H-42

—CH₃ H-43

—CH₃ H-44

—CH₃ H-45

—CH₃ H-46

—CH₃ H-47

—CH₃

Compounds of formula I, whereinA¹ and A² independently from each other are selected from

R⁵ is a group —NR⁸R⁹, wherein R⁸ and R⁹ independently from each otherstand for C₁-C₈-alkyl,A¹, such as

especially

or R⁸ and R⁹ together with the nitrogen atom to which they are bondedform a five or six membered heterocyclic ring which can be condensed byone or two optionally substituted phenyl groups, such as

wherein R¹⁵, R¹⁶ and R¹⁷ independently from each other stands forhydrogen, C₁-C₈-alkyl or C₁-C₈-alkoxy, R^(5″) and R^(6″) independentlyfrom each other stands for hydrogen, C₁-C₈-alkyl or C₁-C₈-alkoxy, andX¹ stands for hydrogen, or C₁-C₈-alkyl, are preferred as guestcompounds.

Particularly preferred guest choromophores of DPP compounds representedby the formula I and IV are the following compounds: Com- pound (of for-mula IV) A⁹ = A¹⁰ R¹³ = R¹⁴ G-1 

—CH₃ G-2  ″ n-C₄H₉ G-3  ″ n-CH₁₂H₂₅ G-4 

G-5 

n-C₄H₉ G-6 

C₂H₅ G-7 

n-C₆H₁₃ G-8 

n-C₆H₁₃ G-9 

n-C₆H₁₃ Com- pound (of for- mula I) A¹ = A² R¹ = R² G-10

n-C₄H₉ G-11

n-C₁₂H₂₅ G-12 ″ n-C₄H₉ G-13

CH₃ G-14

CH₃ G-15 ″ n-C₄H₉ G-16

n-C₄H₉ G-17

n-C₄H₉ G-18

n-C₄H₉ G-19

CH₃ G-20

n-C₄H₉ G-21

n-C₄H₉ G-22

n-C₄H₉ G-23 ″ CH₃ G-24

n-C₄H₉ G-25

n-C₄H₉ G-26 ″ —CH(CH₃)₂ G-27

CH₃ G-28

CH₃ G-29

C₂H₅ G-30

n-C₄H₉ G-31

n-C₄H₉ G-32

n-C₄H₉ G-33

n-C₆H₁₃ G-34

n-C₄H₉

In addition, the compounds of formula I can be used with other knownfluorescent compounds as host or guest compounds, for example, fusedderivatives of aromatic hydrocarbons such as rubrene and perylene; fusedheterocyclics such as pyridinothiadiasole, pyrazolopyridine andnaphtalimide derivatives; rare rare earth complex as Eu, Ir, or Ptcomplex; zincporphyrin, rhodamine, deazafivain derivatives, coumarinederivatives, phenoxazones, quinacridones, dicyanoethenylarenes, Alq₃ andthe derivatives thereof or the pyrromethene metal complexes disclosed inEP-A-1,253,151, JP2001 257077, JP2001 257078, and JP2001 297881.

Particularly preferred inventive host/guest compositions comprisecompounds H-2 and G-12, H-17 and G-12, H-22 and G-12, H-12 and G-28,H-12 and G-30, H-2 and G-13, H-2 and G-33, H-4 and G-13, H-4 and G-33,Alq₃ and G-13 as well as Alq₃ and G-33.

A further embodiment of the present invention is directed todiketopyrrolopyrroles of formula

whereinR²¹ and R²² may be the same or different and are selected from aC₁-C₂₅alkyl group, an allyl group, which can be substituted one to threetimes with C₁-C₄alkyl, a cycloalkyl group, a cycloalkyl group, which canbe condensed one or two times by phenyl which can be substituted one tothree times with C₁-C₄-alkyl, halogen, nitro or cyano, an alkenyl group,a cycloalkenyl group, an alkynyl group, a haloalkyl group, a haloalkenylgroup, a haloalkynyl group, a ketone or aldehyde group, an ester group,a carbamoyl group, a ketone group, a silyl group, a siloxanyl group, A³or —CR³R⁴—(CH₂)_(m)-A³ whereinR³ and R⁴ independently from each other stand for hydrogen orC₁-C₄alkyl, or phenyl which can be substituted one to three times withC₁-C₄alkyl,A³ stands for aryl or heteroaryl, in particular phenyl or 1- or2-naphthyl which can be substituted one to three times with C₁-C₈alkyland/or C₁-C₈alkoxy, and m stands for 0, 1, 2, 3 or 4,A⁷ and A⁸ independently from each other are selected from

A¹ and A² are independently of each other a group,

whereinone of R⁵, R⁶ and R⁷ is a halogen atom, like a chlorine atom, bromineatom, or iodine atom, and the others are as defined above and X¹ is asdefined above. The diketopyrrolopyrroles of formula III are novel andrepresent intermediates In the production of the diketopyrrolopyrrolesof formula I.

A⁷ and A⁸ independently from each other are, preferably, selected from

wherein R⁵ is a chlorine atom or a bromine atom.

The DPP compounds of formula II are described e.g. in U.S. Pat. No.4,579,949, and/or can be prepared according to the method describedtherein (or in U.S. Pat. No. 4,659,775), in which an appropriate nitrileis reacted with a corresponding dialkyl or diaryl succinate, e.g. NC—Ar¹and NC—Ar² are reacted with sodium tert.-amyl alcohol followed by theaddition of diisopropyl succinate.

Compounds I are also available in analogy to the method described inEP-A-353,184, which comprises reacting a DPP compound of formula IIIwith a nucleophilic agent such as a secondary amine, HNR¹²R¹³,preferably in a molar ratio of DPP III:nucleophilic agent in the rangeof 1.2:1 to 0.8:1, or, if R² has the same meaning as R¹ in the range offrom 1:2.5 to 1:1, in the presence of an anhydrous dipolar aproticsolvent, and of an anhydrous base in an amount in the range of fromusually 0.1 to 15 moles per mole of the nucleophilic agent, at atemperature in the range of from usually 100 to 220° C. and under apressure generally in the range of from 100 to 300 kPa (for details seeEP-A-1,087,005).

The DPP compounds of formula III are known and/or can be prepared e.g.according to the method described in EP-A-0353184.

The wording “at least two adjacent substituents form an aromatic oraliphatic fused ring system” means two adjacent substituents can form anaromatic ring, such as a phenyl or naphthyl ring, an aliphatic ring,such as a cyclohexyl ring, or a heterocyclic ring, such as a pyridine orpyrrole ring, wherein two or more of such rings can form a fused ringsystem with the group to which they are bonded.

The term “halogen” means fluorine, chlorine, bromine and iodine.

C₁-C₂₅alkyl is typically linear or branched—where possible—methyl,ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl,n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl,n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl,undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl,preferably C₁-C₈alkyl such as methyl, ethyl, n-propyl, isopropyl,n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl,3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, more preferably C₁-C₄alkylsuch as typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, Isobutyl, tert.-butyl.

The terms “haloalkyl, haloalkenyl and haloalkynyl” mean groups given bypartially or wholly substituting the above-mentioned alkyl group,alkenyl group and alkynyl group with halogen, such as trifluoromethyletc. The “aldehyde group, ketone group, ester group, carbamoyl group andamino group” include those substituted by an alkyl group, a cycloalkylgroup, an aryl group, an aralkyl group or a heterocyclic group, whereinthe alkyl group, the cycloalkyl group, the aryl group, the aralkyl groupand the heterocyclic group may be unsubstituted or substituted. The term“silyl group” means a group of formula —SiR⁶²R⁶³R⁵⁴, wherein R⁶², R⁶³and R⁶⁴ are independently of each other a C₁-C₈alkyl group, inparticular a C₁-C₄ alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, such as a trimethylsilyl group. The term “siloxanyl group” meansa group of formula —O—SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are asdefined above, such as a trimethylsiloxanyl group.

Examples of C₁-C₈alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy,3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy,1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁-C₄alkoxy suchas typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthio group” meansthe same groups as the alkoxy groups, except that the oxygen atom ofether linkage is replaced by a sulfur atom.

The term “aryl group” is typically C₆-C₂₄aryl, such as phenyl,1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, terphenyl, pyrenyl, 2-or 9-fluorenyl or anthracenyl, preferably C₈-C₁₂aryl such as phenyl,1-naphthyl, 2-naphthyl, 4-biphenyl, which may be unsubstituted orsubstituted.

The term “aralkyl group” is typically C₇-C₂₄aralkyl, such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α, α-dimethylbenzyl, ω-phenylbutyl,ω,ω-dimethyl-ω-phenyl-butyl, phenyl-dodecyl, ω-phenyl-octadecyl,ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₆aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl orω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both thealiphatic hydrocarbon group and aromatic hydrocarbon group may beunsubstituted or substituted.

The term “aryl ether group” is typically a C₆₋₂₄aryloxy group, that isto say O—C₆₋₂₄aryl, such as, for example, phenoxy or 4-methoxyphenyl.The term “aryl thioether group” is typically a C₆₋₂₄arylthio group, thatis to say S—C₆₋₂₄aryl, such as, for example, phenylthio or4-methoxyphenylthio. The term “carbamoyl group” is typically aC₁₋₁₈carbamoyl radical, preferably C₁₋₈carbamoyl radical, which may beunsubstituted or substituted, such as, for example, carbamoyl,methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The term “cycloalkyl group” is typically C₅-C₁₂cycloalkyl, such ascyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl,cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted orsubstituted. The term “cycloalkenyl group” means an unsaturatedalicyclic hydrocarbon group containing one or more double bonds, such ascyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may beunsubstituted or substituted. The cycloalkyl group, in particular acyclohexyl group, can be condensed one or two times by phenyl which canbe substituted one to three times with C₁-C₄-alkyl, halogen and cyano.Examples of such condensed cyclohexyl groups are:

in particular

wherein R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and R⁵⁶ are independently of each otherC₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particular hydrogen.

The wording “a group comprising a five-membered heterocyclic ring,containing one to three heteroatoms selected from the group of nitrogen,oxygen and sulfur” means a single five-membered heterocyclic ring, suchas thienyl, furyl, furfuryl, 2H-pyranyl, pyrrolyl, imidazolyl, orpyrazolyl, or a five-membered heterocyclic ring which is part of a fusedring system, which is formed by the five-membered heterocyclic ring witharyl, heteroaryl and/or cycloalkyl groups, which can optionally besubstituted. Examples of such groups are contained in the list of groupsfor A¹ and A² as well as in the definition of heteroaryl or heterocyclicgroups.

The wording “a group comprising a six-membered heterocyclic ring,containing one to three heteroatoms selected from the group of nitrogen,oxygen and sulfur” means a single six-membered heterocyclic ring, suchas pyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, or asix-membered heterocyclic ring which is part of a fused ring system,which is formed by the six-membered heterocyclic ring with aryl,heteroaryl and/or cycloalkyl groups, which can optionally besubstituted. Examples of such groups are contained in the list of groupsfor A¹ and A² as well as in the definition of heteroaryl or heterocyclicgroup.

The term “heteroaryl or heterocyclic group” is a ring with five to sevenring atoms, wherein nitrogen, oxygen or sulfur are the possible heteroatoms, and is typically an unsaturated heterocyclic radical with five to18 atoms having at least six conjugated π-electrons such as thienyl,benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl,2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl,phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl,triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl,indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl,phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl,pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl,phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl,isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl,preferably the above-mentioned mono- or bicyclic heterocyclic radicals.

The terms “aryl” and “alkyl” in alkylamino groups, dialkylamino groups,alkylarylamino groups, arylamino groups and diarylgroups are typicallyC₁-C₂₅alkyl and C₆-C₂₄aryl, respectively.

The above-mentioned groups can be substituted by a C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, acarboxyl group, an ester group, a carbamoyl group, an amino group, anitro group, a silyl group or a siloxanyl group.

The present invention relates further to an electroluminescent devicehaving the fluorescent diketopyrrolopyrroles of formula I or thecompositions according to the present invention between an anode and acathode and emitting light by the action of electrical energy.

Typical constitutions of latest organic electroluminescent devices are:

(i) an anode/a hole transporting layer/an electron transporting layer/acathode, in which the compounds or compositions of the present inventionare used either as positive-hole transport compound or composition,which is exploited to form the light emitting and hole transportinglayers, or as electron transport compounds or compositions, which can beexploited to form the light-emitting and electron transporting layers,

(ii) an anode/a hole transporting layer/a light-emitting layer/anelectron transporting layer/a cathode, in which the compounds orcompositions form the light-emitting layer regardless of whether theyexhibit positive-hole or electron transport properties in thisconstitution,

(iii) an anode/a hole injection layer/a hole transporting layer/alight-emitting layer/an electron transporting layer/a cathode,

(iv) an anode/a hole transporting layer/a light-emitting layer/apositive hole inhibiting layer/an electron transporting layer/a cathode,

(v) an anode/a hole injection layer/a hole transporting layer/alight-emitting layer/a positive hole inhibiting layer/an electrontransporting layer/a cathode,

(vi) an anode/a light-emitting layer/an electron transporting layer/acathode,

(vii) an anode/a light-emitting layer/a positive hole inhibitinglayer/an electron transporting layer/a cathode,

(viii) a mono-layer containing a light emitting material alone or acombination a light emitting material and any of materials of the holetransporting layer, the hole-blocking layer and/or the electrontransporting layer, and

(ix) a multi-layered structure described in (ii) to (vii), wherein alight emitting layer is the monolayer defined in (viii).

The compounds and compositions of the present invention can, Inprincipal be used for any organic layer, such as, for example, holetransporting layer, light emitting layer, or electron transportinglayer, but are preferably used as the light emitting material in thelight emitting layer.

Thin film type electroluminescent devices usually consist essentially ofa pair of electrodes and at least one charge transporting layer inbetween. Usually two charge transporting layers, a hole transportinglayer (next to the anode) and an electron transporting layer (next tothe cathode) are present. Either one of them contains—depending on itsproperties as hole-transporting or electron-transporting material—aninorganic or organic fluorescence substance as light-emitting material.It is also common, that a light-emitting material is used as anadditional layer between the hole-transporting and theelectron-transporting layer. In the above mentioned device structure, ahole injection layer can be constructed between an anode and a holetransporting layer and/or a positive hole inhibiting layer can beconstructed between a light emitting layer and an electron transportinglayer to maximise hole and electron population in the light emittinglayer, reaching large efficiency In charge recombination and intensivelight emission.

The devices can be prepared in several ways. Usually, vacuum evaporationis used for the preparation. Preferably, the organic layers arelaminated in the above order on a commercially availableindium-fin-oxide (“ITO”) glass substrate held at room temperature, whichworks as the anode in the above constitutions. The membrane thickness ispreferably in the range of 1 to 10,000 nm, more preferably 1 to 5,000nm, more preferably 1 to 1,000 nm, more preferably 1 to 500 nm. Thecathode metal, such as a Mg/Ag alloy, a binary Li—Al or LiF—Al systemwith an thickness In the range of 50-200 nm is laminated on the top ofthe organic layers. The vacuum during the deposition is preferably lessthan 0.1333 Pa (1×10⁻³ Torr), more preferably less than 1.333×10⁻³ Pa(1×10⁻⁵ Torr), more preferably less than 1.333×10⁻⁴ Pa (1×10⁻⁶ Torr).

As anode usual anode materials which possess high work function such asmetals like gold, silver, copper, aluminum, indium, Iron, zinc, tin,chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungstenand the like, metallic alloys such as magnesium/copper,magnesium/silver, magnesium/aluminum, aluminum/indium and the like,semiconductors such as Si, Ge, GaAs and the like, metallic oxides suchas indium-tin-oxide (“ITO”), ZnO and the like, metallic compounds suchas CuI and the like, and furthermore, electroconducting polymers suchpolyacetylene, polyaniline, polythiophene, polypyrrole,polyparaphenylene and the like, preferably ITO, most preferably ITO onglass as substrate can be used.

Of these electrode materials, metals, metallic alloys, metallic oxidesand metallic compounds can be transformed into electrodes, for example,by means of the sputtering method. In the case of using a metal or ametallic alloy as a material for an electrode, the electrode can beformed also by the vacuum deposition method. In the case of using ametal or a metallic alloy as a material forming an electrode, theelectrode can be formed, furthermore, by the chemical plating method(see for example, Handbook of Electrochemistry, pp 383-387, Mazuren,1985). In the case of using an electroconducting polymer, an electrodecan be made by forming it into a film by means of anodic oxidationpolymerization method onto a substrate which is previously provided withan electroconducting coating. The thickness of an electrode to be formedon a substrate is not limited to a particular value, but, when thesubstrate is used as a light emitting plane, the thickness of theelectrode is preferably within the range of from 1 nm to 300 nm, morepreferably, within the range of from 5 to 200 nm so as to ensuretransparency.

In a preferred embodiment ITO is used on a substrate having an ITO filmthickness in the range of from 10 nm (100 Å) to 1μ (10000 Å), preferablyfrom 20 nm (200 Å) to 500 nm (5000 Å). Generally, the sheet resistanceof the ITO film is chosen in the range of not more than 100 Ω/cm²,preferably not more than 50 Ω/cm².

Such anodes are commercially available from Japanese manufacturers, suchas Geomatech Co. Ltd., Sanyo Vacuum Co. Ltd., Nippon Sheet Glass Co.Ltd.

As substrate either an electronconducting or electrically insulatingmaterial can be used. In case of using an electroconducting substrate, alight emitting layer or a positive hole transporting layer is directlyformed thereupon, while in case of using an electrically insulatingsubstrate, an electrode is firstly formed thereupon and then a lightemitting layer or a positive hole transporting layer is superposed.

The substrate may be either transparent, semi-transparent or opaque.However, in case of using a substrate as an indicating plane, thesubstrate must be transparent or semi transparent.

Transparent electrically insulating substrates are, for example,inorganic compounds such as glass, quartz and the like, organicpolymeric compounds such as polyethylene, polypropylene,polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate,polyvinylchloride, polyvinylalcohol, polyvinylacetate and the like. Eachof these substrates can be transformed into a transparentelectroconducting substrate by providing it with an electrode accordingto one of the methods described above.

Examples of semitransparent electrically insulating substrates areinorganic compounds such as alumina, YSZ (yttrium stabilized zirconia)and the like, organic polymeric compounds such as polyethylene,polypropylene, polystyrene, epoxy resins and the like. Each of thesesubstrates can be transformed into a semitransparent electroconductingsubstrate by providing it with an electrode according to one of theabovementioned methods.

Examples of opaque electroconducting substrates are metals such asaluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper,silver, gold, platinum and the like, various elctroplated metals,metallic alloys such as bronze, stainless steel and the like,semiconductors such as Si, Ge, GaAs, and the like, electroconductingpolymers such as polyaniline, polythiophene, polypyrrole, polyacetylene,polyparaphenylene and the like.

A substrate can be obtained by forming one of the above listed substratematerials to a desired dimension. It is preferred that the substrate hasa smooth surface. Even, if it has a rough surface, it will not cause anyproblem for practical use, provided that it has round unevenness havinga curvature of not less than 20 μm. As for the thickness of thesubstrate, there is no restriction as far as it ensures sufficientmechanical strength.

As cathode usual cathode materials which possess low work function suchas alkali metals, earth alkaline metals, group 13 elements, silver, andcopper as well as alloys or mixtures thereof such as sodium, lithium,potassium, calcium, lithium fluoride (LiF), sodium-potassium alloy,magnesium, magnesium-silver alloy, magnesium-copper alloy,magnesium-aluminum alloy, magnesium-indium alloy, aluminum,aluminum-aluminum oxide alloy, aluminum-lithium alloy, Indium, calcium,and materials exemplified in EP-A 499,011 such as electroconductingpolymers e.g. polypyrrole, polythiophene, polyaniline, polyacetyleneetc., preferably Mg/Ag alloys, LiF—Al or Li—Al compositions can be used.

In a preferred embodiment a magnesium-silver alloy or a mixture ofmagnesium and silver, or a lithium-aluminum alloy, lithiumfluoride-aluminum alloy or a mixture of lithium and aluminum can be usedin a film thickness in the range of from 10 nm (100 Å) to 1 μm (10000Å), preferably from 20 nm (200 Å) to 500 nm (5000 Å).

Such cathodes can be deposited on the foregoing electron transportinglayer by known vacuum deposition techniques described above.

In a preferred ambodiment of this invention a light-emitting layer canbe used between the hole transporting layer and the electrontransporting layer. Usually the light-emitting layer is prepared byforming a thin film on the hole transporting layer.

As methods for forming said thin film, there are, for example, thevacuum deposition method, the spin-coating method, the casting method,the Langmuir-Blodgett (“LB”) method and the like. Among these methods,the vacuum deposition method, the spin-coating method and the castingmethod are particularly preferred in view of ease of operation and cost.

In case of forming a thin film using a composition by means of thevacuum deposition method, the conditions under which the vacuumdeposition is carried out are usually strongly dependent on theproperties, shape and crystalline state of the compound(s). However,optimum conditions are usually as follows: temperature of the heatingboat: 100 to 400° C.; substrate temperature: −100 to 350° C.; pressure:1.33×10⁴ Pa (1×10² Torr) to 1.33×10⁻⁴ Pa (1×10⁻⁶ Torr) and depositionrate: 1 pm to 6 nm/sec.

In an organic EL element, the thickness of the light emitting layer isone of the factors determining its light emission properties. Forexample, if a light emitting layer is not sufficiently thick, a shortcircuit can occur quite easily between two electrodes sandwiching saidlight emitting layer, and therefor, no EL emission is obtained. On theother hand, if the light emitting layer is excessively thick, a largepotential drop occurs Inside the light emitting layer because of itshigh electrical resistance, so that the threshold voltage for ELemission increases. Accordingly, the thickness of the organic lightemitting layer is limited to the range of from 5 nm to 5 μm, preferablyto the range of from 10 nm to 500 nm.

In the case of forming a right emitting layer by using the spin-coatingmethod and the casting method, ink jet printing method, the coating canbe carried out using a solution prepared by dissolving the compositionin a concentration of from 0.0001 to 90% by weight in an appropriateorganic solvent such as benzene, toluene, xylene, tetrahydrofurane,methyltetrahydrofurane, N,N-dimethylformamide, dichloromethane,dimethylsulfoxide and the like. If the concentration exceeds 90% byweight, the solution usually is so viscous that it no longer permitsforming a smooth and homogenous film. On the other hand, if theconcentration is less than 0.0001% by weight, the efficiency of forminga film is too law to be economical. Accordingly, a preferredconcentration of the composition is within the range of from 0.01 to 80%by weight.

In the case of using the above spin-coating or casting method, it ispossible to further improve the homogeneity and mechanical strength ofthe resulting layer by adding a polymer binder to the solution forforming the light emitting layer. In principle, any polymer binder maybe used, provided that it is soluble in the solvent in which thecomposition is dissolved. Examples of such polymer binders arepolycarbonate, polyvinylalcohol, polymethacrylate,polymethylmethacrylate, polyester, polyvinylacetate, epoxy resin and thelike. However, if the solid content composed of the polymer binder andthe composition exceeds 99% by weight, the fluidity of the solution isusually so low that it is impossible to form a light emitting layerexcellent in homogeneity. On the other hand, if the content of thecomposition is substantially smaller than that of the polymer binder,the electrical resistance of said layer is very large, so that it doesnot emit light unless a high voltage is applied thereto. Accordingly,the preferred ratio of the polymer binder to the composition is chosenwithin the range of from 10:1 to 1:50 by weight, and the solid contentcomposed of both components in the solution is preferably within therange of from 0.01 to 80% by weight, and more preferably, within therange of 0.1 to 60% by weight.

As hole-transporting layers known organic hole transporting compoundssuch as polyvinyl carbazole

a TPD compound disclosed in J. Amer. Chem. Soc. 90 (1968) 3925:

wherein Q₁ and Q₂ each represent a hydrogen atom or a methyl group;a compound disclosed in J. Appl. Phys. 65(9) (1989) 3610:

a stilbene based compound

wherein T and T₁ stand for an organic radical;a hydrazone based compound

wherein Rx, Ry and Rz stand for an organic radical, and the like can beused.

Compounds to be used as a positive hole transporting material are notrestricted to the above listed compounds. Any compound having a propertyof transporting positive holes can be used as a positive holetransporting material such as triazole derivatives, oxadiazolederivatives, imidazole derivatives, polyarylalkane derivatives,pyrazoline derivative, pyrazolone derivatives, phenylene diaminederivatives, arylamine derivatives, amino substituted chalconederivatives, oxazole derivatives, stilbenylanthracene derivatives,fluorenone derivatives, hydrazone derivatives, stilbene derivatives,copolymers of aniline derivatives, PEDOT(poly(3,4-ethylenedioxy-thiophene)) and the derivatives thereof,electro-conductive oligomers, particularly thiophene oligomers,porphyrin compounds, aromatic tertiary amine compounds, stilbenyl aminecompounds etc.

Particularly, aromatic tertiary amine compounds such asN,N,N′,N′-tetraphenyl-4,4′-diaminobiphenyl,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-4,4′-diaminobiphenyl (TPD),2,2′-bis(diptorylaminophenyl)propane,1,1′-bis(4-di-torylaminophenyl)-4phenylcyclohexane,bis(4-dimethylamino-2-methylphenyl)phenylmethane,bis(4-di-p-tolylaminophenyl)phenylmethane,N,N′-diphenyl-N,N′-dl(4-methoxyphenyl)-44′-diaminobiphenyl,N,N,N′,N′-tetraphenyl-4,4′-diaminodiphenylether,4,4′-bis(diphenylamino)quaterphenyl, N,N,N-tri(p-tolyl)amine,4-(di-p-tolylamino)-4′-[4-(di-p-tolylamino)stilyl]stilbene,4-N,N-diphenylamino-(2-diphenylvinyl)benzene,3-methoxy-4′-N,N-diphenylaminostilbene, N-phenylcarbazole etc. are used.

Furthermore, 4,4′-bis[N-(1-naphtyl)-N-phenylamino]biphenyl disclosed inU.S. Pat. No. 5,061,569 and the compounds disclosed in EP-A 508,562, inwhich three triphenylamine units are bound to a nitrogen atom, such as4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine, can beused.

A positive hole transporting layer can be formed by preparing an organicfilm containing at least one positive hole transporting material on theanode. The positive hole transporting layer can be formed by the vacuumdeposition method, the spin-coating method, the casting method, ink jetprinting method, the LB method and the like. Of these methods, thevacuum deposition method, the spin-coating method and the casting methodare particularly preferred in view of ease and cost.

In the case of using the vacuum deposition method, the conditions fordeposition may be chosen In the same manner as described for theformation of a light emitting layer (see above). If it is desired toform a positive hole transporting layer comprising more than onepositive hole transporting material, the coevaporation method can beemployed using the desired compounds.

In the case of forming a positive hole transporting layer by thespin-coating method or the casting method, the layer can be formed underthe conditions described for the formation of the light emitting layer(see above).

As in the case of forming the light emitting layer a smoother and morehomogeneous positive hole transporting layer can be formed by using asolution containing a binder and at least one positive hole transportingmaterial. The coating using such a solution can be performed in the samemanner as described for the light emitting layer. Any polymer binder maybe used, provided that it is soluble in the solvent in which the atleast one positive hole transporting material is dissolved. Examples ofappropriate polymer binders and of appropriate and preferredconcentrations are given above when describing the formation of a lightemitting layer.

The thickness of the positive hole transporting layer is preferablychosen in the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm,more preferably from 2 to 50 nm.

As hole injection materials known organic hole transporting compoundssuch as metal-free phthalocyanine (H₂Pc), copper-phthalocyanine (Cu-Pc)and their derivatives as described, for example, in JP64-7635 can beused. Furthermore, some of the aromatic amines defined as holetransporting materials above, which have a lower ionisation potentialthan the hole transporting layer, can be used.

A hole injection layer can be formed by preparing an organic filmcontaining at least one hole injection material between the anode layerand the hole transporting layer. The hole injection layer can be formedby the vacuum deposition method, the spin-coating method, the castingmethod, the LB method and the like. The thickness of the layer ispreferably from 5 nm to 5 μm, and more preferably from 10 nm to 100 nm.

The electron transporting materials should have a high electroninjection efficiency (from the cathode) and a high electron mobility.The following materials can be exemplified for electron transportingmaterials: tris(8-hydroxyquinolinato)-aluminum(III) and its derivatives,bis(10-hydroxybenzo[h]quinolinolato)beryllium(II) and its derivatives,oxadiazole derivatives, such as2-(4-biphenyl)-5-(4-tert.-butylphenyl)-1,3,4-oxadiazole and its dimersystems, such as1,3-bis(4-tert.-butylphenyl-1,3,4)oxadiazolyl)biphenylene and1,3-bis(4-tert.-butylphenyl-1,3,4-oxadiazolyl)phenylene, dioxazolederivatives, triazole derivatives, coumarine derivatives,imidazopyridine derivatives, phenanthroline derivatives or perylenetetracarboxylic acid derivatives disclosed in Appl. Phys. Lett. 48 (2)(1986) 183.

An electron transporting layer can be formed by preparing an organicfilm containing at least one electron transporting material on the holetransporting layer or on the light-emitting layer. The electrontransporting layer can be formed by the vacuum deposition method, thespin-coating method, the casting method, the LB method and the like.

It is preferred that the positive hole inhibiting materials for apositive hole inhibiting layer have high electron injection/transportingefficiency from the electron transporting layer to the light emissionlayer and also have higher ionisation potential than the light emittinglayer to prevent the flowing out of positive holes from the lightemitting layer to avoid a drop in luminescence efficiency.

As the positive hole inhibiting material known materials, such as Balq,TAZ and phenanthroline derivatives, e.g. bathocuproine (BCP), can beused:

The positive hole inhibiting layer can be formed by preparing an organicfilm containing at least one positive hole inhibiting material betweenthe electron transporting layer and the light-emitting layer. Thepositive hole inhibiting layer can be formed by the vacuum depositionmethod, the spin-coating method, the casting method, ink jet printingmethod, the LB method and the like. The thickness of the layerpreferably is chosen within the range of from 5 nm to 2 μm, and morepreferably, within the range of from 10 nm to 100 nm.

As in the case of forming a light emitting layer or a positive holetransporting layer, a smoother and more homogeneous electrontransporting layer can be formed by using a solution containing a binderand at least one electron transporting material.

The thickness of an electron transporting layer is preferably chosen inthe range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, morepreferably from 2 to 50 nm.

In general, the host chromphore is a diketopyrrolopyrrole having aphotoluminescence emission peak at 500 to 720 nm, preferably 520 to 630nm, most preferred 540 to 600 nm. The host chromphore is preferably adiketopyrrolopynrole of formula II.

The light-emitting compositions have a fluorescence emission maximum inthe range of from 500 to 780, preferably from 520 to 750, more preferredfrom 540 to 700 nm. Further, the inventive compounds preferably exhibitan absorption maximum in the range of 450 to 600 nm.

The light-emitting compositions usually exhibit a fluorescence quantumyield (“FQY”) in the range of from 1>FQY≧0.3 (measured in aeratedtoluene or DMF). Further, in general, the inventive compositions exhibita molar absorption coefficient In the range of from 5000 to 100000.

Another embodiment of the present invention relates to a method ofcoloring high molecular weight organic materials (having a molecularweight usually in the range of from 10³ to 10⁷ g/mol; comprisingbiopolymers, and plastic materials, including fibres) by incorporatingtherein the inventive compounds or compositions by methods known in theart.

The inventive compounds and compositions can be used, as described forthe DPP compounds of formula I′ In EP-A-1087005, for the preparation of

-   inks, for printing inks in printing processes, for flexographic    printing, screen printing, packaging printing, security ink    printing, intaglio printing or offset printing, for pre-press stages    and for textile printing, for office, home applications or graphics    applications, such as for paper goods, for example, for ballpoint    pens, felt tips, fiber tips, card, wood, (wood) stains, metal,    inking pads or inks for impact printing processes (with    impact-pressure ink ribbons), for the preparation of-   colorants, for coating materials, for industrial or commercial use,    for textile decoration and Industrial marking, for roller coatings    or powder coatings or for automotive finishes, for high-solids    (low-solvent), water-containing or metallic coating materials or for    pigmented formulations for aqueous paints, for the preparation of-   pigmented plastics for coatings, fibers, platters or mold carriers,    for the preparation of-   non-impact-printing material for digital printing, for the thermal    wax transfer printing process, the ink jet printing process or for    the thermal transfer printing process, and also for the preparation    of-   color filters, especially for visible light in the range from 400 to    700 nm, for liquid-crystal displays (LCDs) or charge combined    devices (CCDs) or for the preparation of-   cosmetics or for the preparation of-   polymeric ink particles, toners, dye lasers, dry copy toners liquid    copy toners, or electrophotographic toners, and electroluminescent    devices.

Another preferred embodiment concerns the use of the inventive compoundsand compositions for color changing media. There are three majortechniques in order to realize full-color organic electroluminescentdevices:

(i) use of the three primary colors blue, green and red generated byelectroluminescence,

(ii) conversion of the electroluminescent blue or white tophotoluminescent green and red via color changing media (CCM), whichabsorb the above electroluminescent blue, and fluorescence in green andred.

(iii) conversion of the white luminescent emission to blue, green andred via color filters.

The inventive compounds or compositions are useful for EL materials forthe above category (i) and, in addition, for the above mention technique(ii). This is because the invented compounds or compositions can exhibitstrong photoluminescence as well as electroluminescence.

Technique (ii) is, for example, known from U.S. Pat. No. 5,126,214,wherein EL blue with a maximum wavelength of ca. 470-480 nm is convertedto green and red using coumarin,4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran,pyridine, rhodamine 6G, phenoxazone or other dyes.

The inventive compounds or compositions are useful for EL materials forthe above category (iii) as an element of white luminescent incombination of other compensatory electroluminescence to construct whiteluminescent. This is because compounds or compositions can exhibitstrong photoluminescence as well as electrolunimescence.

Illustrative examples of suitable organic materials of high molecularweight which can be colored with the inventive compositions aredescribed in EP-A-1087005.

Particularly preferred high molecular weight organic materials, inparticular for the preparation of a paint system, a printing ink or ink,are, for example, cellulose ethers and esters, e.g. ethylcellulose,nitrocellulose, cellulose acetate and cellulose butyrate, natural resinsor synthetic resins (polymerization or condensation resins) such asaminoplasts, in particular urea/formaldehyde and melamine/formaldehyderesins, alkyd resins, phenolic plastics, polycarbonates, polyolefins,polystyrene, polyvinyl chloride, polyamides, poly-urethanes, polyester,ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone andsilicone resins as well as their possible mixtures with one another.

It is also possible to use high molecular weight organic materials indissolved form as film formers, for example boiled linseed oil,nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde andurea/formaldehyde resins as well as acrylic resins.

Said high molecular weight organic materials may be obtained singly orin admixture, for example in the form of granules, plastic materials,melts or in the form of solutions, in particular for the preparation ofspinning solutions, paint systems, coating materials, inks or printinginks.

In a particularly preferred embodiment of this invention, the inventivecompounds and compositions are used for the mass coloration of polyvinylchloride, polyamides and, especially, polyolefins such as polyethyleneand polypropylene as well as for the preparation of paint systems,including powder coatings, inks, printing inks, color filters andcoating colors.

Illustrative examples of preferred binders for paint systems arealkyd/melamine resin paints, acryl/melamine resin paints, celluloseacetate/cellulose butyrate paints and two-pack system lacquers based onacrylic resins which are crosslinkable with polyisocyanate.

Hence, another embodiment of the present invention relates to acomposition comprising

-   (a) 0.01 to 50, preferably 0.01 to 5, particularly preferred 0.01 to    2% by weight, based on the total weight of the coloured high    molecular organic material, of a fluorescent diketopyrrolopyrrole    according to formula I or of a composition according to the present    invention, and-   (b) 99.99 to 50, preferably 99.99 to 95, particularly preferred    99.99 to 98% by weight, based on the total weight of the coloured    high molecular organic material, of a high molecular organic    material, and    (c) optionally, customary additives such as rheology improvers,    dispersants, fillers, paint auxiliaries, siccatives, plasticizers,    UV-stabilizers, and/or additional pigments or corresponding    precursors in effective amounts, such as e.g. from 0 to 50% by    weight, based on the total weight of (a) and (b).

To obtain different shades, the inventive fluorescent DPP compounds offormula I or the inventive compositions may advantageously be used inadmixture with fillers, transparent and opaque white, colored and/orblack pigments as well as customary luster pigments in the desiredamount.

For the preparation of paints systems, coating materials, color filters,inks and printing inks, the corresponding high molecular weight organicmaterials, such as binders, synthetic resin dispersions etc. and theinventive compounds or compositions are usually dispersed or dissolvedtogether, if desired together with customary additives such asdispersants, fillers, paint auxiliaries, siccatives, plasticizers and/oradditional pigments or pigment precursors, in a common solvent ormixture of solvents. This can be achieved by dispersing or dissolvingthe individual components by themselves, or also several componentstogether, and only then bringing all components together, or by addingeverything together at once.

Hence, a further embodiment of the present invention relates to a methodof using the inventive compounds or compositions for the preparation ofdispersions and the corresponding dispersions, and paint systems,coating materials, color filters, inks and printing inks comprising theinventive compositions.

A particularly preferred embodiment relates to the use of the inventivecompounds or compositions for the preparation of fluorescent tracers fore.g. leak detection of fluids such as lubricants, cooling systems etc.,as well as to fluorescent tracers or lubricants comprising the inventivecompositions.

For the pigmentation of high molecular weight organic material, theinventive compounds or compositions, optionally in the form ofmasterbatches, are mixed with the high molecular weight organicmaterials using roll mills, mixing apparatus or grinding apparatus.Generally, the pigmented material is subsequently brought into thedesired final form by conventional processes, such as calandering,compression molding, extrusion, spreading, casting or injection molding.

For pigmenting lacquers, coating materials and printing inks the highmolecular weight organic materials and the inventive compounds orcompositions, alone or together with additives, such as fillers, otherpigments, siccatives or plasticizers, are generally dissolved ordispersed in a common organic solvent or solvent mixture. In this caseit is possible to adopt a procedure whereby the individual componentsare dispersed or dissolved individually or else two or more aredispersed or dissolved together and only then are all of the componentscombined.

The present invention additionally relates to inks comprising acoloristically effective amount of the pigment dispersion of theinventive compositions.

The weight ratio of the pigment dispersion to the ink in general ischosen in the range of from 0.001 to 75% by weight, preferably from 0.01to 50% by weight, based on the overall weight of the ink.

The preparation and use of color filters or color-pigmented highmolecular weight organic materials are well-known in the art anddescribed e.g. in Displays 14/2, 1151 (1993), EP-A 784085, or GBA2,310,072.

The color filters can be coated for example using inks, especiallyprinting inks, which can comprise pigment dispersions comprising theinventive compositions or can be prepared, for example, by mixing apigment dispersion comprising an inventive composition with chemically,thermally or photolytically structurable high molecular weight organicmaterial (so-called resist). The subsequent preparation can be carriedout, for example, in analogy to EP-A 654 711 by application to asubstrate, such as a LCD (liquid crystal display), subsequentphotostructuring and development.

Particular preference for the production of color filters is given topigment dispersions comprising an inventive compound or compositionwhich possess non-aqueous solvents or dispersion media for polymers.

The present invention relates, moreover, to toners comprising a pigmentdispersion containing an inventive compound or composition or a highmolecular weight organic material pigmented with an Inventivecomposition in a coloristically effective amount.

The present invention additionally relates to colorants, coloredplastics, polymeric ink particles, or non-impact-printing materialcomprising an inventive composition, preferably in the form of adispersion, or a high molecular weight organic material pigmented withan inventive composition in a coloristically effective amount.

A coloristically effective amount of the pigment dispersion according tothis invention comprising an inventive composition denotes in generalfrom 0.0001 to 99.99% by weight, preferably from 0.001 to 50% by weightand, with particular preference, from 0.01 to 50% by weight, based onthe overall weight of the material pigmented therewith.

The inventive compositions can be applied to colour polyamides, becausethey do not decompose during the incorporation into the polyamides.Further, they exhibit an exceptionally good lightfastness, a superiorheat stability, especially in plastics.

The organic EL device of the present invention has significantindustrial values since it can be adapted for a flat panel display of anon-wall television set, a flat light-emitting device, a light source fora copying machine or a printer, a light source for a liquid crystaldisplay or counter, a display signboard and a signal light. Thecompounds and compositions of the present invention can be used in thefields of an organic EL device, an electrophotographic photoreceptor, aphotoelectric converter, a solar cell, an image sensor, and the like.

The following examples are for illustrative purposes only and are not tobe construed to limit the scope of the instant invention in any mannerwhatsoever. In the examples the “parts” denote parts by weight and the“percentages” denote “percentages by weight”, unless otherwise stated.

EXAMPLE 1

3.8 g of sodium and 300 ml of tert-amyl alcohol are heated up to 100° C.under a nitrogen atmosphere and stirred for 15 hours. The reactionmixture is allowed to cool to room temperature. 27.7 g of2-cyano-5-bromopyridine are added and heated up to 110° C. As soon asthe temperature has been reached, a solution of 16.2 g of diisopropylsuccinate and 100 ml of tert-amyl alcohol is added over 1 hour using adropping funnel. When the addition has been completed, the reactionmixture is kept for 20 hours at 100° C. and cooled down to 65° C. Then300 ml of water are added and the resultant pigment suspension isfiltered at room temperature, washed with methanol and water untilwashings run colorless and dried at 100° C. in vacuum, affording 6.6 g(9.8% of theory, based on dibutyl succinate) of1,4-diketo-3,6-bis-2-(5-bromopyridin-yl)-pyrrolo-(3,4-c)-pyrrole.

2.0 g of1,4-diketo-3,6-bis-2-(5-bromopyridine-yl)-pyrrolo-(3,4-c)-pyrrole areslurred in 1-methyl 2-pyrrolidinone for 2 hours at room temperature. 1.5g of potassium tert-butoxide are added to the slurry under nitrogen.After stirred for 3 hours, 2.4 g of n-butyl iodide are added to thereaction mixture and agitated additional 18 hours. Then, the mixture ispoured into 50 ml of water and the precipitate is collected byfiltration and purified by column chromatography (silica gel,dichloromethane as eluant), followed by washing with methanol.

After drying 450 mg of2,5,-dibutyl-1,4,-diketo-3,6-bis-2-(5-bromopyridine-yl)pyrrolo(3,4,-c)pyrrole are obtained (yield 18%).

EXAMPLE 2

200 mg of2,5-di-butyl-1,4,-diketo-3,6-bis-2-(5-bromopyridine-yl)pyrrolo(3,4,-c)pyrrole, 151 mg of diphenylamine, 6 mg of palladium(II)acetate, 20 mg ofbis-diphenylphosphino ferrocene, 233 mg of cesium carbonate and 50 ml ofdry xylene are placed in a three necked flask and stirred at 150° C.under nitrogen for 7 hours. After the completion of the reaction, xyleneis removed under reduced pressure and the residue is purified by columnchromatography (silica gel, dichloromethane as eluant) After drying,0.12 g (46%) of the desired product are obtained as red solid.

EXAMPLE 3

Example 1 is repeated except that methyl iodide is used in place ofbutyl iodide. A red solid (yield: 18%) is obtained.

EXAMPLE 4

220 mg of 2,5-dimethyl-1,4-diketo-3,6-bis-2-(5-bromopyridin-yl)pyrrolo(3,4,-c) pyrrole, 228 mg of ditolylamine, 6 mg ofpalladium(II)acetate, 20 mg of bis-diphenylphosphino ferrocene, 300 mgof cesium carbonate and 10 ml of dry xylene are placed in a three neckedflask and stirred at 150° C. under nitrogen for 4 hours. Aftercompletion of the reaction, xylene is removed under reduced pressure andthe residue is purified by column chromatography (silica gel,dichloromethane as eluant) After drying, 0.08 g (24%) of the desiredproduct are obtained as red solid.

EXAMPLE 5

6.01 g of sodium and 400 ml of tert-amyl alcohol are heated up to 100°C. under a nitrogen atmosphere and stirred for 18 hours. The reactionmixture is allowed to cool to room temperature, 44.66 g of2-cyano-5-bromothiophene are added and heated up to 110° C. As soon asthe temperature has been reached, a solution of 24.3 g of diisopropylsuccinate and 100 ml of tert-amyl alcohol is added over 5 hours using adropping funnel. When the addition has been completed, the reactionmixture is kept for 20 hours at 120° C. and cooled down to 65° C. Then300 ml of water and 20 ml of acetic acid are added and the resultantpigment suspension is filtered at room temperature, washed with methanoland water until washings run colorless, and dried, affording 8.0 g 7.3%of theory, based on dibutyl succinate) of1,4-diketo-3,6-bis-2-(5-bromothiophene-yl)-pyrrolo-(3,4-c)-pyrrole.

Example 3 is repeated, except using A-4 in place of A-1, whereby a redsolid is obtained (yield: 5%).

EXAMPLE 6

200 mg of A-5, 150 mg of 3,5-dimethylphenylboronic acid, 10 mg oftetrakis-(triphenylphosphino)palladium, 166 mg of potassium carbonateand 10 ml of dry xylene are placed in a three-necked flask and stirredat 130° C. for 1 hour. The xylene is removed and the resultant productis purified by column chromatography (silica gel, dichroromethane aseluant). After drying, 0.02 g of the desired product (A-8) are obtainedas purple solid.

EXAMPLE 7

Example 5 is repeated, except using 2-cyano-3,4-ethylenedioxythiophenein place of 2-cyano-5-bromothiophene, whereby a dark purple solid isobtained (yield: 15%).

Example 3 is repeated, except that A-7 is used in place of A-3, wherebya red solid is obtained (yield: 25%).

EXAMPLE 8

Example 4 is repeated, except that A-5 is used in place of A-3, wherebya red purple solid is obtained (yield: 10%).

EXAMPLE 9

Example 1 is repeated except that n-dodecyl iodide is used in place ofbutyl iodide. A red solid (yield: 13%) is obtained.

EXAMPLE 10

Example 4 is repeated, except that A-10 and diphenylamine are used inplace of A-3 and ditolylamine, respectively, whereby a purple solid isobtained (yield: 21%).

EXAMPLE 11

Example 1 is repeated, except that 2-cyanopyridine is used in place of2-cyano-5-bromopyridine, whereby a red solid is obtained (yield: 32%).

Example 3 is repeated, except that A-11 is used in place of A-1 wherebya red solid is obtained (yield: 69%). TABLE 1 A-12

Physical properties Absorption¹⁾ PL²⁾ Example Peak Peak Mp.³⁾ No.Compound (nm) (nm) [° C.]  1 A-1  523, 8330⁴⁾  545 300<  1 A-2  546,21942   575 231-233  2 G-12 586, 61662   606 295-301  3 A-3  543, 5079   572 >300  4 G-13 585, 74649   613 >300  5 A-4  — — >300  6 A-5  570,49003   588, 631 >300  7 A-6  602, 19655   624 >300  8 A-7  544, 26802⁴⁾552 >300  9 A-8  511, 12283   564 292-295 10 A-9  614, 61308   651131-139 11 A-10 547, 13654   577 151-153 12 G-11 584, 54820   609169-170 13 A-11 511, 16685⁴⁾ 530 >300 14 A-12 529, 12174   558 298-300¹⁾In toluene;²⁾photoluminescence in toluene;³⁾melting point;⁴⁾in DMF.

APPLICATION EXAMPLE 1

Luminescent Element 1

A glass substrate (manufactured by Geomatek Co., a product prepared byelectron beam vapor deposition method) on which an ITO transparentelectroconductive film has been deposited up to a thickness of ca. 120nm is cut into a size of 30×40 mm, and etched. The substrate thusobtained is subjected to ultrasonic washing with Semikoklin® 56 for 15minutes, and then washed with hot ultra-pure water. Subsequently, thesubstrate is subjected to ultrasonic washing with acetone for 15minutes, and then dried. Just before forming the substrate Into anelement, the substrate thus obtained is subjected to an air plasmatreatment for half an hour and placed in a vacuum vapor depositionapparatus. The apparatus is evacuated until the inner pressure reached1×10⁻⁵ Pa or less. Then, according to the resistance heating method, aphthalocyanine copper complex (CuPc) is vapor-deposited up to athickness of 20 nm to form a positive hole Injection layer.N,N′-Di(naphthalen-1-y)-N,N′-diphenyl-benzidine (α-NPD) isvapor-deposited up to a thickness of 40 nm, to form a positive holetransporting layer. Subsequently, the DPP compound H-2 as host and theDPP compound G-13 (obtained in example 4) are co-deposited up to athickness of 30 nm as guest as a light emitting layer, wherein the ratioof the DPP compounds is controlled by the deposition rate(H-2:G-13=100:1-0.5), to form a uniform light emitting layer.Subsequently, an Alq₃ layer having a thickness of 30 nm isvapor-deposited to form an electron transporting layer. Lithium fluoride(LiF) of thickness of 0.5 nm is vapor-deposited as electron injectionmaterial. On top of the electron injection material, aluminium (Al of athickness of 150 nm is vapor-deposited to form a cathode, and an elementhaving a size of 2×2 mm square is prepared.

The luminescent peak wavelength and emission intensity of theluminescent element 1 thus obtained is summarized in Table 1.

Application Example 1 is repeated to prepare luminescent elements 2 to4. The light emitting materials used are specified in table 2 below.TABLE 2 Light Emitting Material EL properties Luminescent Host GuestPeak Intensity Element (99 wt %) (ca. 1 wt %) (nm) (cd/m²) 1 H-2  G-13632  4308 2 H-2  G-12 624 16090 3 H-17 G-12 623  6929 4 H-22 G-12 61616710 Reference Compound 1 578  4386 (100 wt %)¹⁾ ¹⁾Compound 1 below(cf. example 81 in EP-A1087006) is used as light emitting material.

As evident from the EL properties of the luminescent elements thepresent invention can provide luminescent elements high in theefficiency of electrical energy utilisation and high in luminance.

EXAMPLE 12

The fluorescent dye A-12 and PMMA was dissolved in dichloromethane and a3 mm diameter quarts rod is dipped into the solution, forming a thinfilm around the quarts rod. The sample is dried in a drying oven for 6hours. The concentration of the A-12 in the PMMA film is 2 mM/l. Theprepared quarts rod is used as a ring resonator and the light amplifierof the thin-film ring laser system.

The thin film ring laser is composed of two components. One is thequarts rod with a dye doped PMMA thin film, which works as a ringresonator. And the other is a planner waveguide made from a PMMA thinfilm. The pumping source is a third harmonic generation of a pulsedNd:YAG laser; its wavelength is 355 nm and it's pulse width is 7 ns.When the pumping beam (083 mJ/cm²) operates yellow laser oscillationwith a centre wavelength of the laser at 530 nm is observed.

EXAMPLE 13

Example 1 was repeated except that n-hexyl iodide was used in place ofbutyl iodide (yield: 6%). Mp.=196-199° C.

EXAMPLE 14

Example 4 was repeated except that A-13 was used in place of A-3 (yield:45%). Mp.=268-270° C.

Luminescent Elements 5 and 6

Application Example 1 is repeated to prepare luminescent elements 5 and6. The light emitting materials used are specified in table 3 below.TABLE 3 Light Emitting Material EL properties Luminescent Host GuestPeak Intensity Element (99 wt %) (ca. 1 wt %) (nm) (cd/m²) 5 H-2  G-33620 17405 6 Alq₃ G-33 626  5670

1. A fluorescent diketopyrrolopyrrole of formula I

wherein R¹ and R² may be the same or different and are a C₁-C₂₅alkylgroup, which can be substituted by fluorine, chlorine or bromine, anallyl group, which can be substituted one to three times withC₁-C₄alkyl, a cycloalkyl group, a cycloalkyl group, which can becondensed one or two times by phenyl which can be substituted one tothree times with C₁-C₄-alkyl, halogen, nitro or cyano, an alkenyl group,a cycloalkenyl group, an alkynyl group, a haloalkyl group, a haloalkenylgroup, a haloalkynyl group, a ketone or aldehyde group, an ester group,a carbamoyl group, a ketone group, a silyl group, a siloxanyl group, A³or —CR³R⁴—(CH₂)_(m)-A³ wherein R³ and R⁴ independently from each otherstand for hydrogen or C₁-C₄alkyl, or phenyl which can be substituted oneto three times with C₁-C₄alkyl, A³ stands for aryl or heteroaryl, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, and m stands for 0, 1, 2, 3 or 4, A¹ and A² areindependently of each other a group comprising a five-memberedheterocyclic ring, containing one to three heteroatoms selected from thegroup of nitrogen, oxygen and sulfur, or a six-membered heterocyclicring, containing one to three heteroatoms selected from the group ofnitrogen, oxygen and sulfur, wherein, if A¹ and A² are a single five- orsix-membered heterocyclic ring of formula

said heterocyclic ring is substituted by at least a group selected froma C₁-C₂₅alkyl group, a cycloalkyl group, an aralkyl group, an alkenylgroup, a cycloalkenyl group, an alkynyl group, a hydroxyl group, amercapto group, an alkoxy group, an alkylthio group, an aryl ethergroup, an aryl thioether group, an aryl group, a heterocyclic group, ahalogen atom, a haloalkyl group, a haloalkenyl group, a haloalkynylgroup, a cyano group, an aldehyde group, a carboxyl group, an estergroup, a carbamoyl group, an amino group, a nitro group, a silyl group,a siloxanyl group, a substituted or unsubstituted vinyl group, a groupNR⁸R⁹, wherein R⁸ and R⁹ independently of each other stand for ahydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, aheteroaryl group, a heterocyclic group, an aralkyl group, or R⁸ and R⁹together with the nitrogen atom to which they are bonded form a five orsix membered heterocyclic ring, which can be condensed by one or twooptionally substituted phenyl groups, wherein the heterocyclic ring isdirectly bonded to the DPP basis unit, A¹ and A² are independently ofeach other a group

wherein R⁵, R⁶, and R⁷ may be the same or different and are a hydrogenatom, a C₁-C₂₅alkyl group, a cycloalkyl group, an aralkyl group, analkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group,a mercapto group, an alkoxy group, an alkylthio group, an aryl ethergroup, an aryl thioether group, an aryl group, a heterocyclic group, ahalogen atom, a haloalkyl group, a haloalkenyl group, a haloalkynylgroup, a cyano group, an aldehyde group, a carboxyl group, an estergroup, a carbamoyl group, a nitro group, a silyl group, a siloxanylgroup, a substituted or unsubstituted vinyl group, a group NR⁸R⁹,wherein R⁸ and R⁹ independently of each other stand for a hydrogen atom,an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, aheterocyclic group, an aralkyl group, or R⁸ and R⁹ together with thenitrogen atom to which they are bonded form a five or six memberedheterocyclic ring, which can be condensed by one or two optionallysubstituted phenyl groups, or at least two adjacent substituents R⁵ toR⁷ form an aromatic or aliphatic fused ring system, and X¹ is a hydrogenatom, a C₁-C₂₅alkyl group, a cycloalkyl group, an aralkyl group, an arylgroup, or a heterocyclic group, wherein at least one of the groups R⁵,R⁶, and R⁷ is different from a hydrogen atom, if A¹ and A² are a singlefive- or six-membered heterocyclic ring, containing one heteroatomselected from the group of nitrogen, oxygen and sulfur, with theproviso, that the following compounds are excluded


2. A fluorescent diketopyrrolopyrrole according to claim 1, wherein R¹and R² independently from each other are C₁-C₈alkyl, C₅-C₁₂-cycloalkyl,which can be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, or C₅-C₁₂cycloalkyl, which can be condensed one or twotimes by phenyl which can be substituted one to three times withC₁-C₄-alkyl, halogen, nitro or cyano, phenyl or 1- or 2-naphthyl whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, or —CR³R⁴—-(CH₂)_(m)-A³ wherein R³ and R⁴ stand forhydrogen, A³ stands for phenyl or 1- or 2-naphthyl, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and mstands for 0 or
 1. 3. A fluorescent diketopyrrolopyrrole according toclaim 1, wherein A¹ and A² independently from each other are

wherein R⁵ is a hydrogen atom, a C₁-C₁₂alkyl group, a C₁-C₈alkoxy group,a group of formula

or a group —NR⁸R⁹, wherein R⁸ and R⁹ independently from each other standfor C₁-C₈alkyl group,

R⁸ and R⁹ together with the nitrogen atom to which they are bonded forma five or six membered heterocyclic ring which can be condensed by oneor two optionally substituted phenyl groups, wherein R¹⁵, R¹⁶ and R¹⁷independently from each other stands for hydrogen, C₁-C₈-alkyl,C₁-C₈-alkoxy, or phenyl, R^(5′) is R⁵, except hydrogen, R^(5″) andR^(6″) independently from each other stands for hydrogen, C₁-C₈-alkyl orC₁-C₈-alkoxy, and X¹ stands for hydrogen, or C₁-C₈-alkyl.
 4. Afluorescent diketopyrrolopyrrole according to claim 3, which is

R¹ and R² are independently of each other a C₁-C₁₂alkyl group, aC₅-C₇cycloalkyl group, which optionally can be substituted by one tothree C₁-C₈-alkyl or C₁-C₈-alkoxy groups, a C₅-C₇cycloalkyl group, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, or which can be condensed one or two times by optionallysubstituted phenyl, or a C₇-C₁₄aralkylgroup, which optionally can besubstituted by one to three C₁-C₈-alkyl or C₁-C₈-alkoxy groups, and R¹⁵and R¹⁶ stands for hydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, or phenyl.
 5. Acomposition comprising a guest chromophore and a host chromophore,wherein the absorption spectrum of the guest chromophore overlaps withthe fluorescence emission spectrum of the host chromophore, wherein thehost chromophore is a diketopyrrolopyrrole having a photoluminescenceemission peak at 500 to 720 nm and wherein the host choromophore and/orthe guest chromophore is a diketopyrrolopyrrole of formula I accordingto claim
 1. 6. A composition comprising a guest chromophore and a hostchromophore, wherein the absorption spectrum of the guest chromophoreoverlaps with the fluorescence emission spectrum of the hostchromophore, wherein the host chromophore is a diketopyrrolopyrrolehaving a photoluminescence emission peak at 500 to 720 nm and whereinthe guest chromophore is a diketopyrrolopyrrole of formula I accordingto claim
 1. 7. A composition according to claim 6, wherein the hostchromophore is a diketopyrrolopyrrole (“DPP”) represented by formula II

wherein R¹³ and R¹⁴ independently from each other stand forC₁-C₂₅-alkyl, which can be substituted by fluorine, chlorine or bromine,C₅-C₁₂-cycloalkyl or C₅-C₁₂-cycloalkyl, which can be condensed one ortwo times by phenyl which can be substituted one to three times withC₁-C₄-alkyl, halogen, nitro or cyano, silyl, A⁶ or—CR¹¹R¹²—(CH₂)_(m)-A⁶, wherein R¹¹ and R¹² independently from each otherstand for hydrogen, fluorine, chlorine, bromine, cyano or C₁-C₄alkyl,which can be substituted by fluorine, chlorine or bromine, or phenylwhich can be substituted one to three times with C₁-C₄alkyl, A⁶ standsfor phenyl or 1- or 2-naphthyl which can be substituted one to threetimes with C₁-C₈alkyl, C₁-C₈alkoxy, halogen, nitro, cyano, phenyl, whichcan be substituted with C₁-C₈alkyl or C₁-C₈alkoxy one to three times,—NR²³R²⁴, wherein R²³ and R²⁴ represent hydrogen, C₁-C₂₅-alkyl,C₅-C₁₂-cycloalkyl or C₆-C₂₄-aryl, in particular phenyl or 1- or2-naphthyl which can be substituted one to three times with C₁-C₈alkyl,C₁-C₈alkoxy, halogen or cyano, or phenyl, which can be substituted withC₁-C₈alkyl or C₁-C₈alkoxy one to three times, and m stands for 0, 1, 2,3 or 4, A⁴ and A⁵ independently from each other stand for

wherein R²⁵, R²⁶, R²⁷ independently from each other stands for hydrogen,C₁-C₂₅alkyl, —CR¹¹R¹²—(CH₂)_(m)-A⁶, cyano, halogen, —OR²⁹, —S(O)_(p)R³⁰,or phenyl, which can be substituted one to three times with C₁-C₈alkylor C₁-C₈alkoxy, wherein R²⁹ stands for C₁-C₂₅-alkyl, C₅-C₁₂-cycloalkyl,—CR¹¹R¹²—(CH₂)_(m)-Ph, C₆-C₂₄-aryl, or a saturated or unsaturatedheterocyclic radical comprising five to seven ring atoms, wherein thering consists of carbon atoms and one to three hetero atoms selectedfrom the group consisting of nitrogen, oxygen and sulfur, R³⁰ stands forC₁-C₂₅-alkyl, C₅-C₁₂-cycloalkyl, —CR¹¹R¹²—(CH₂)_(m)-Ph, R²⁸ stands forC₂-C₂₀-heteroaryl or C₆-C₂₄-aryl, p stands for 0, 1, 2 or 3, m and nstands for 0, 1, 2, 3 or
 4. 8. A composition according to claim 7,wherein R¹³ and R¹⁴ independently from each other stand for C₁-C₈alkyl,C₅-C₁₂-cycloalkyl, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy, phenyl or 1- or 2-naphthyl which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, or—CR¹¹R¹²—(CH₂)_(m)-A⁶ wherein R¹¹ and R¹² stand for hydrogen, orC₁-C₄alkyl, A⁶ stands for phenyl or 1- or 2-naphthyl, which can besubstituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy, and mstands for 0 or
 1. 9. A composition according to claim 7, wherein A⁴ andA⁵ independently from each other stand for

wherein R²⁵ is C₁-C₈-alkyl, phenyl, 1- or 2-naphthyl.
 10. An EL devicecomprising a fluorescent diketopyrrolopyrrole according to claim
 1. 11.A diketopyrrolopyrrole of formula III

wherein R²¹ and R²² may be the same or different and are a C₁-C₂₅alkylgroup, an allyl group, which can be substituted one to three times withC₁-C₄alkyl, a cycloalkyl group, a cycloalkyl group, which can becondensed one or two times by phenyl which can be substituted one tothree times with C₁-C₄-alkyl, halogen, nitro or cyano, an alkenyl group,a cycloalkenyl group, an alkynyl group, a haloalkyl group, a haloalkenylgroup, a haloalkynyl group, a ketone or aldehyde group, an ester group,a carbamoyl group, a ketone group, a silyl group, a siloxanyl group, A³or —CR³R⁴—(CH₂)_(m)-A³ wherein R³ and R⁴ independently from each otherstand for hydrogen or C₁-C₄alkyl, or phenyl which can be substituted oneto three times with C₁-C₄alkyl, A³ stands for aryl or heteroaryl, whichcan be substituted one to three times with C₁-C₈alkyl and/orC₁-C₈alkoxy, and m stands for 0, 1, 2, 3 or 4, A⁷ and A⁸ independentlyfrom each other are selected from

A⁷ and A⁸ are independently of each other a group

wherein wherein one of R⁵, R⁶ and R⁷ is a halogen atom, and the othersare as defined in claim 1 and X¹ is as defined in claim
 1. 12. Adiketopyrrolopyrrole of formula III according to claim 11, wherein A⁷and A⁸ independently from each other are

wherein R⁵ is a chlorine atom or a bromine atom and X¹ is as defined inclaim
 1. 13. Composition comprising (a) 99.99 to 50% by weight of a highmolecular weight organic material, based on the total weight of thecolored high molecular weight organic material, (b) 0.01 to 50% weightof a fluorescent diketopyrrolopyrrole according to claim 1, based on thetotal weight of the colored high molecular weight organic material and(c) if desired, customary additives in effective amounts.
 14. (canceled)15. Composition comprising (a) 99.99 to 50% by weight of a highmolecular weight organic material, based on the total weight of thecolored high molecular weight organic material, (b) 0.01 to 50% weightof a composition according to claim 5, based on the total weight of thecolored high molecular weight organic material and (c) if desired,customary additives in effective amounts.
 16. A fluorescent tracer,color changing medium, solid dye laser, or EL device comprising afluorescent diketopyrrolopyrrole according to claim
 1. 17. A fluorescenttracer, color changing medium, solid dye laser, or EL device comprisinga composition according to claim
 5. 18. A fluorescentdiketopyrrolopyrrole according to claim 1, wherein A¹ and A² areindependently of each other


19. A fluorescent diketopyrrolopyrrole according to claim 4, which is


20. A composition according to claim 5, wherein the host chromophore isa diketopyrrolopyrrole having a photoluminescence emission peak at 520to 630 nm.
 21. A composition according to claim 6, wherein the hostchromophore is a diketopyrrolopyrrole having a photoluminescenceemission peak at 520 to 630 nm.